有机光氧化还原催化实现的炔烃的发散性功能化
Divergent Functionalization of Alkynes Enabled by Organic Photoredox Catalysis.
作者信息
Zhu Zhengbo, Qian Siran, Nicewicz David A
机构信息
Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina, 27599-3290, USA.
出版信息
Synlett. 2023 Jun;34(9):1023-1028. doi: 10.1055/a-2009-8279. Epub 2023 Jan 31.
Abstract
Direct functionalization of alkynes under oxidative conditions is challenging, as alkynes are usually recalcitrant towards typical oxidants. Herein, we communicate a strategy for the divergent functionalization of alkynes with photoexcited acridinium organic dyes, presumably via the formation of vinyl cation radicals as key intermediates. Based on the nature of the nucleophiles, different types of difunctionalized products were obtained in moderate to good yields. Addition of lithium Lewis acids resulted in a surprising reversal of diastereocontrol.
摘要
在氧化条件下实现炔烃的直接官能团化具有挑战性，因为炔烃通常对典型的氧化剂具有抗性。在此，我们报道了一种利用光激发的吖啶鎓有机染料对炔烃进行发散式官能团化的策略，推测其关键中间体为乙烯基阳离子自由基。根据亲核试剂的性质，以中等至良好的产率获得了不同类型的双官能化产物。加入锂路易斯酸导致了非对映选择性的惊人反转。
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